U.S. patent number 10,035,875 [Application Number 15/452,711] was granted by the patent office on 2018-07-31 for patterned film structure, patterned film composite structure, method of selective inhibition of formation of organic film and method of selective adjustment of thickness of organic film.
This patent grant is currently assigned to MAY-HWA ENTERPRISE CORPORATION. The grantee listed for this patent is MAY-HWA ENTERPRISE CORPORATION. Invention is credited to Hsien-Yeh Chen, Chih-Yu Wu.
United States Patent |
10,035,875 |
Chen , et al. |
July 31, 2018 |
Patterned film structure, patterned film composite structure,
method of selective inhibition of formation of organic film and
method of selective adjustment of thickness of organic film
Abstract
A patterned film structure consists of a substrate and of a
patterned polymeric layer which selectively covers and exposes part
of the surface of the substrate. The patterned polymeric layer is
selected form at least one of an unsubstituted poly-para-xylylene
and a substituted poly-para-xylylene.
Inventors: |
Chen; Hsien-Yeh (Taipei,
TW), Wu; Chih-Yu (Taipei, TW) |
Applicant: |
Name |
City |
State |
Country |
Type |
MAY-HWA ENTERPRISE CORPORATION |
Taipei |
N/A |
TW |
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Assignee: |
MAY-HWA ENTERPRISE CORPORATION
(Taipei, TW)
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Family
ID: |
60483466 |
Appl.
No.: |
15/452,711 |
Filed: |
March 7, 2017 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20170349697 A1 |
Dec 7, 2017 |
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Foreign Application Priority Data
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Jun 2, 2016 [TW] |
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105117310 A |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G
61/02 (20130101); C09D 165/00 (20130101); C09D
165/04 (20130101); C23C 16/04 (20130101); B05D
1/60 (20130101); C08G 2261/312 (20130101); C08G
2261/3326 (20130101); C08G 2261/146 (20130101); C08G
2261/143 (20130101); C08G 2261/1414 (20130101); C08G
2261/11 (20130101); C08G 2261/3424 (20130101); C08G
2261/124 (20130101); C08G 2261/1428 (20130101); C08G
2261/149 (20130101) |
Current International
Class: |
C08G
61/02 (20060101); C09D 165/00 (20060101); C23C
16/04 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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101255658 |
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Sep 2008 |
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CN |
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103608067 |
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Feb 2014 |
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CN |
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Other References
Xing Yu-mei et al., Microfabrication of multichannel flexible
neural microelectrodes, Optics and Precision Engineering, vol. 17,
No. 10, Oct. 2009, p. 2465-2472,
www.eope.net/fileup/PDF/2008-0896.pdf. cited by applicant.
|
Primary Examiner: Mulvaney; Elizabeth Evans
Attorney, Agent or Firm: Hsu; Winston
Claims
What is claimed is:
1. A patterned film structure, consisting of a substrate and a
patterned polymeric layer which selectively covers a surface of
said substrate, wherein said patterned polymeric layer consists of
an unsubstituted poly-para-xylylene or of a substituted
poly-para-xylylene to selectively expose said surface of said
substrate and said patterned polymeric layer is a co-polymer
selected from monomers consisting of an unsubstituted
poly-para-xylylene monomer and a substituted poly-para-xylylene
monomer.
2. The patterned film structure of claim 1, wherein said substrate
is selected from a group consisting of an insulator and of a
conductor.
3. The patterned film structure of claim 1, wherein said
substituted poly-para-xylylene is a poly-para-xylylene substituted
with an unsaturated bond, halogen, an aldehyde group, an alkyl
group substituted with a hydroxyl group, a halo-alkyl group, a
4-trifluoroacetyl group, an amino-alkyl group, an amide group, an
amide group comprising a disulfide bond, a carboxyl group, a
biotinyl group, an N-hydroxysuccinimdyl group, an N-maleimide or a
carboxyl anhydride.
4. The patterned film structure of claim 1, wherein said patterned
polymeric layer has a thickness from 5 nm to 100 .mu.m.
5. A patterned film composite structure, comprising: a substrate; a
conductor layer selectively covering the surface of said substrate;
and a patterned polymeric layer together with said conductor layer
to completely cover the surface of said substrate, wherein said
patterned polymeric layer consists of an unsubstituted
poly-para-xylylene or a substituted poly-para-xylylene.
6. The patterned film composite structure of claim 5, wherein said
substrate is a patterned substrate.
7. The patterned film structure of claim 5, wherein said patterned
polymeric layer is a co-polymer selected from monomers consisting
of an unsubstituted poly-para-xylylene monomer and a substituted
poly-para-xylylene monomer.
8. The patterned film structure of claim 5, wherein said
substituted poly-para-xylylene is a poly-para-xylylene substituted
with an unsaturated bond, a halogen, an aldehyde group, an alkyl
group substituted with a hydroxyl group, a halo-alkyl group, a
4-trifluoroacetyl group, an amino-alkyl group, an amide group, an
amide group comprising a disulfide bond, a carboxyl group, a
biotinyl group, an N-hydroxysuccinimdyl group, an N-maleimide or a
carboxyl anhydride.
9. The patterned film structure of claim 5, wherein said patterned
polymeric layer covers said conductor layer.
10. The patterned film structure of claim 9, wherein said patterned
polymeric layer has a variable thickness from 5 nm to 100
.mu.m.
11. The patterned film structure of claim 5, wherein said patterned
polymeric layer does not cover said conductor layer.
12. The patterned film structure of claim 11, wherein said
patterned polymeric layer has a variable thickness from 5 nm to 100
.mu.m.
13. A method to selectively inhibit the formation of an organic
film, comprising: providing a substrate; and providing a precursor
under a pre-determined condition so that said precursor forms an
organic film on said substrate and said organic film consists of an
unsubstituted poly-para-xylylene or a substituted
poly-para-xylylene, wherein said pre-determined condition
selectively inhibits the formation of said organic film so that
said organic film forms a given pattern which selectively covers
said substrate and selectively exposes the surface of said
substrate.
14. The method to selectively inhibit the formation of an organic
film of claim 13, wherein said substrate is selected from a group
consisting of a conductor, an insulator and combinations thereof,
and said organic film does not cover said conductor.
15. The method to selectively inhibit the formation of an organic
film of claim 13, wherein said pre-determined condition is selected
from a group consisting of adjusting voltage, adjusting a charge
density, adjusting a deposition rate, adjusting the ingredient of
said precursor, adjusting the formation time of selectively
inhibiting, adjusting the formation temperature of selectively
inhibiting and adjusting the composition of said substrate.
16. The method to selectively inhibit the formation of an organic
film of claim 13, wherein said organic film is a co-polymer
selected from monomers consisting of an unsubstituted
poly-para-xylylene monomer and a substituted poly-para-xylylene
monomer.
17. The method to selectively inhibit the formation of an organic
film of claim 16, wherein said substituted poly-para-xylylene is a
poly-para-xylylene substituted with an unsaturated bond, a halogen,
an aldehyde group, an alkyl group substituted with a hydroxyl
group, a halo-alkyl group, a 4-trifluoroacetyl group, an
amino-alkyl group, an amide group, an amide group comprising a
disulfide bond, a carboxyl group, a biotinyl group, an
N-hydroxysuccinimdyl group, an N-maleimide or a carboxyl
anhydride.
18. The method to selectively inhibit the formation of an organic
film of claim 16, wherein said organic film has a thickness from 5
nm to 100 .mu.m.
19. A method to selectively adjust the thickness of an organic
film, comprising: providing a substrate comprising a patterned
conductor layer which is exposed; and providing a precursor under a
pre-determined condition so that said precursor forms an organic
film completely covering said substrate and said organic film is
selected from a group consisting of an unsubstituted
poly-para-xylylene and a substituted poly-para-xylylene, wherein
said organic film forms a given pattern of a thickness which is
variable on said substrate.
20. The method to selectively adjust the thickness of an organic
film of claim 19, wherein said substrate is selected from a group
consisting of said patterned conductor layer and of an insulator,
and said thickness on said insulator is greater than that on said
patterned conductor layer.
21. The method to selectively adjust the thickness of an organic
film of claim 19, wherein said pre-determined condition is selected
from a group consisting of adjusting voltage, adjusting a charge
density, adjusting a deposition rate, adjusting the ingredient of
said precursor, adjusting the formation time of selectively
inhibiting, adjusting the formation temperature of selectively
inhibiting and adjusting the composition of said substrate.
22. The method to selectively adjust the thickness of an organic
film of claim 19, wherein said substituted poly-para-xylylene is a
poly-para-xylylene substituted with an unsaturated bond, a halogen,
an aldehyde group, an alkyl group substituted with a hydroxyl
group, a halo-alkyl group, a 4-trifluoroacetyl group, an
amino-alkyl group, an amide group, an amide group comprising a
disulfide bond, a carboxyl group, a biotinyl group, an
N-hydroxysuccinimdyl group, an N-maleimide or a carboxyl anhydride.
Description
CROSS REFERENCE TO RELATED APPLICATION
This application claims priority from Taiwanese Patent Application
No. 105117310, filed on Jun. 2, 2016, the contents of which are
hereby incorporated by reference in their entirety for all
purposes.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to a patterned film
structure, to a patterned film composite structure, to a method to
selectively inhibit the formation of an organic film and to a
method to selectively adjust the thickness of an organic film. In
particular, the present invention is directed to a method to
selectively inhibit the formation of an organic film to obtain a
patterned poly-para-xylylene film structure, or directed to
obtaining a patterned poly-para-xylylene film composite structure
by using a method to selectively adjust a thickness of a target
organic film.
2. Description of the Prior Art
Modern trends in biotechnology fields, such as biomaterials,
biosensors, biochips, microfluidics, drug delivery, tissue
engineering, cellular biology, and regenerative medicine, have
targeted controlled designs to mimic and to respond to the
biological environments on a molecular scale. The key factor that
determines the long term performance as well as high efficiency of
biomaterials relies on the surface modification of
bio-substrates.
In conventional biomaterial research, the chemical vapor deposition
(CVD) is regarded as one of the best synthesizing systems to
prepare poly-para-xylylenes. The resultant prepared
poly-para-xylylenes have the characteristics of good
biocompatibility, good biostability, good moisture-proofing, good
chemical resistance, and dielectric property.
However, the current art mainly resides in providing a
poly-para-xylylene film to completely cover a substrate or an
article. When it comes to a substrate or to an article with an
exposed sensor or with an exposed electrode, nevertheless, the
complete coverage of the resultant poly-para-xylylene film thereon
obviously interferes with the operation of the exposed sensor or
the exposed electrode. Nonetheless, currently there is no simple
approach available to form a poly-para-xylylene film with any given
pattern.
SUMMARY OF THE INVENTION
Given the above, the present invention proposes a patterned film
structure, a patterned film composite structure, a method to
selectively inhibit the formation of an organic film and a method
to selectively adjust the thickness of an organic film. On one
hand, the patterned film structure or the patterned film composite
structure has a patterned poly-para-xylylene film to expose any
given region. On the other hand, the present invention provides a
method to selectively inhibit the formation of an organic film or a
method to selectively adjust the thickness of an organic film to be
able to manipulate the poly-para-xylylene to form a specific
pattern, in particular a pattern of extremely small critical
dimension, on a substrate or on an article. This is a break-through
technique to expand the application of an unsubstituted
poly-para-xylylene or of a substituted poly-para-xylylene so that
the poly-para-xylylene film is capable of combining with various
devices or articles to provide a surface-modified bio-substrate
system.
In a first aspect, the present invention proposes a patterned film
structure. The patterned film structure consists of a substrate and
of a patterned polymeric layer. The patterned polymeric layer
selectively covers the surface of the substrate. The patterned
polymeric layer consists of at least one of an unsubstituted
poly-para-xylylene and of a substituted poly-para-xylylene to
selectively expose the surface of the substrate.
In one embodiment of the present invention, the substrate is
selected from a group consisting of a conductor and of an
insulator.
In another embodiment of the present invention, the patterned
polymeric layer is a co-polymer. The co-polymer is selected from
monomers consists of at least one of an unsubstituted
poly-para-xylylene monomer and of a substituted poly-para-xylylene
monomer.
In another embodiment of the present invention, the substituted
poly-para-xylylene is a poly-para-xylylene substituted with an
unsaturated bond, halogen, an aldehyde group, an alkyl group
substituted with a hydroxyl group, a halo-alkyl group, a
4-trifluoroacetyl group, an amino-alkyl group, an amide group, an
amide group comprising a disulfide bond, a carboxyl group, a
biotinyl group, an N-hydroxysuccinimdyl group, an N-maleimide or a
carboxyl anhydride.
In another embodiment of the present invention, the patterned
polymeric layer has a thickness from 5 nm to 100 .mu.m.
In a second aspect, the present invention proposes a patterned film
composite structure. The patterned film composite structure
includes a substrate, a conductor layer and a patterned polymeric
layer. The conductor layer selectively covers the surface of the
substrate. The patterned polymeric layer together with the
conductor layer completely covers the surface of the substrate. The
patterned polymeric layer consists of at least one of an
unsubstituted poly-para-xylylene and of a substituted
poly-para-xylylene.
In one embodiment of the present invention, the substrate is a
patterned substrate.
In another embodiment of the present invention, the patterned
polymeric layer is a co-polymer. The co-polymer is selected from
monomers consists of at least one of an unsubstituted
poly-para-xylylene monomer and of a substituted poly-para-xylylene
monomer.
In another embodiment of the present invention, the substituted
poly-para-xylylene is a poly-para-xylylene substituted with an
unsaturated bond, a halogen, an aldehyde group, an alkyl group
substituted with a hydroxyl group, a halo-alkyl group, a
4-trifluoroacetyl group, an amino-alkyl group, an amide group, an
amide group comprising a disulfide bond, a carboxyl group, a
biotinyl group, an N-hydroxysuccinimdyl group, an N-maleimide or a
carboxyl anhydride.
In another embodiment of the present invention, the patterned
polymeric layer may cover the conductor layer or not.
In another embodiment of the present invention, the patterned
polymeric layer has a variable thickness from 5 nm to 100
.mu.m.
In a third aspect, the present invention provides a method to
selectively inhibit the formation of an organic film. First, a
substrate or an article is provided. Second, a precursor, such as a
monomer with a para-xylylene moiety is provided under a
pre-determined condition so that the precursor forms an organic
film on the substrate or on the article. The organic film consists
of at least one of an unsubstituted poly-para-xylylene and of a
substituted poly-para-xylylene. The pre-determined condition favors
the selective inhibition of the formation of the organic film so
that the organic film forms a given pattern which selectively
covers the surface of the substrate or the article and the organic
film selectively exposes the surface of the substrate or the
article.
In one embodiment of the present invention, the substrate is
selected from a group consisting of a conductor and of an
insulator. The organic film does not cover the conductor.
In another embodiment of the present invention, the pre-determined
condition is selected from a group consisting of adjusting voltage,
adjusting a charge density, adjusting a deposition rate, adjusting
the ingredient of the precursor, adjusting the formation time of
selectively inhibiting, adjusting the formation temperature of
selectively inhibiting and adjusting the composition of the
substrate.
In another embodiment of the present invention, the organic film is
a co-polymer. The co-polymer consists of at least one of an
unsubstituted poly-para-xylylene monomer and of a substituted
poly-para-xylylene monomer.
In another embodiment of the present invention, the substituted
poly-para-xylylene is a poly-para-xylylene substituted with an
unsaturated bond, a halogen, an aldehyde group, an alkyl group
substituted with a hydroxyl group, a halo-alkyl group, a
4-trifluoroacetyl group, an amino-alkyl group, an amide group, an
amide group comprising a disulfide bond, a carboxyl group, a
biotinyl group, an N-hydroxysuccinimdyl group, an N-maleimide or a
carboxyl anhydride.
In another embodiment of the present invention, the organic film
has a thickness from 5 nm to 100 .mu.m.
In a fourth aspect, the present invention proposes a method to
selectively adjust the thickness of an organic film. First, a
substrate or an article is provided. The substrate or the article
includes a patterned conductor layer which is exposed. Second, a
precursor is provided under a pre-determined condition so that the
precursor forms an organic film. The organic film completely covers
the substrate or the article. The organic film is selected from a
group consisting of an unsubstituted poly-para-xylylene and of a
substituted poly-para-xylylene. The organic film forms a given
pattern of a thickness which is variable on the substrate or the
article.
In one embodiment of the present invention, the substrate is
selected from a group consisting of the patterned conductor layer
and an insulator. The thickness on the insulator is greater than
that on the patterned conductor layer.
In another embodiment of the present invention, the pre-determined
condition is selected from a group consisting of adjusting voltage,
adjusting a charge density, adjusting a deposition rate, adjusting
the ingredient of the precursor, adjusting the formation time of
selectively inhibiting, adjusting the formation temperature of
selectively inhibiting and adjusting the composition of the
substrate.
In another embodiment of the present invention, the substituted
poly-para-xylylene is a poly-para-xylylene substituted with an
unsaturated bond, a halogen, an aldehyde group, an alkyl group
substituted with a hydroxyl group, a halo-alkyl group, a
4-trifluoroacetyl group, an amino-alkyl group, an amide group, an
amide group comprising a disulfide bond, a carboxyl group, a
biotinyl group, an N-hydroxysuccinimdyl group, an N-maleimide or a
carboxyl anhydride.
These and other objectives of the present invention will no doubt
become obvious to those of ordinary skill in the art after reading
the following detailed description of the preferred embodiment that
is illustrated in the various figures and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 to FIG. 4 illustrate a method to manipulate the formation of
an organic film of the present invention.
FIG. 1 illustrates a conductor has a pattern to be embedded in the
insulator.
FIG. 1A illustrates a conductor has a pattern to cover the outer
surface of an insulator.
FIG. 1B illustrates a conductor has a pattern embedded in and
covering the insulator.
FIG. 2 illustrates the substrate is placed in a reaction chamber to
undergo a predetermined polymeric deposition reaction under a
suitable condition with a suitable precursor.
FIG. 2A illustrates a polymeric deposition device to perform the
predetermined polymeric deposition reaction.
FIG. 3 illustrates a method to selectively inhibit the formation of
an organic film of the present invention.
FIG. 4 illustrates a method to selectively adjust the thickness of
an organic film of the present invention.
FIG. 5 and FIG. 5A respectively illustrate the Fourier transform
infrared reflection absorption spectroscopy (IRRAS) spectra of
PPX-C and PPX-aldehyde of the present invention which is unable to
form an organic film on the surfaces of various metals at a charge
density.
FIG. 6 illustrates a correlation of the maximum selective
deposition thickness at different charge density of the PPX-C
organic film and the PPX-aldehyde organic film of the present
invention.
FIG. 7 illustrates a correlation between the deposition rate of the
PPX-C organic film as well as the PPX-aldehyde organic film and the
maximum selective deposition thickness under the influence of an
electric field of the present invention.
FIG. 8 illustrates the deposition results of the PPX-C organic film
of the present invention on different metal surfaces.
FIG. 8A illustrates the deposition results of the PPX-aldehyde
organic film of the present invention on different metal
surfaces.
FIG. 9 illustrates the deposition results of an organic film of
PPX-TFA of the present invention on different conductor surfaces in
the absence of the influence of charge density.
FIG. 9A illustrates different deposition results of an organic film
of PPX-TFA of the present invention on different conductor surfaces
in the presence of the influence of charge density.
FIG. 10 illustrates the deposition results of an organic film of
PPX-amine of the present invention on different conductor surfaces
in the absence of the influence of charge density.
FIG. 10A illustrates the different deposition results of an organic
film of PPX-amine of the present invention on different conductor
surfaces in the presence of the influence of charge density.
FIG. 11 illustrates patterned poly-para-xylylene organic films
which correspond to PPX-TFA, PPX-amine, PPX-aldehyde and PPX-C on a
substrate with patterned Al layer.
FIG. 12 illustrates a method to strip the conductor layer which is
not covered by the organic film of the present invention after the
organic film is formed.
FIG. 13 illustrates a patterned film structure without a conductor
after the stripping step.
FIG. 14 illustrates a patterned film composite structure with the
organic film not covering the conductor.
FIG. 15 illustrates a patterned film structure with a conductor
sandwiched between the insulator and the organic film.
FIG. 16 illustrates the Formula (1) to represent the substituted
para-xylylene precursor.
FIG. 17 illustrates the chemical synthesis of the Reaction (1), the
Reaction (2) and the Reaction (3).
FIG. 18 shows the spectrum of the co-polymer and individual
comparison with the reference spectra of three different functional
groups.
FIG. 19 shows Table 1 of X-ray photoelectron spectroscopy analysis
of the obtained co-polymer organic film.
FIG. 20 is a .sup.1H NMR spectrum of
4-(3-((3-methylamido)-disulfide) propanoic
acid)[2,2]paracyclophane.
FIG. 21 is a .sup.13C NMR spectrum of
4-(3-((3-methylamido)-disulfide) propanoic
acid)[2,2]paracyclophane.
FIG. 22 is a FT-IR spectrum of 4-(3-((3-methylamido)-disulfide)
propanoic acid)[2,2]paracyclophane.
FIG. 23 is an ESI-MS spectrum of 4-(3-((3-methylamido)-disulfide)
propanoic acid)[2,2]paracyclophane.
DETAILED DESCRIPTION
Examples and embodiments are given to further describe various
modes of the present invention. In the specification, the term
"step" is not only for an independent step. It does not exclude the
condition where the expected effect of the step is satisfied.
In the disclosure, the chemical structure of a compound is
sometimes represented by a skeleton formula, in which carbon atoms,
hydrogen atoms and carbon-hydrogen bonds may be optionally omitted.
However, it should be based on the plotted version when a
functional group is clearly depicted in a structure.
In the disclosure, ranges defined by "a numerical value to another
numerical value" are shorthand representations used to avoid
listing all of the numerical values in the specification.
Therefore, the recitation of a specific numerical range is
equivalent to the recitation of any and all numerical values in
that numerical range and discloses a smaller numerical range
defined by any two numerical values in that numerical range, as is
the case with the numerical value and the smaller numerical range
being disclosed in the specification.
The present invention in a first aspect provides a method to
manipulate the formation of an organic film. Such method is not
only able to manipulate if an organic film is formed in a given
region or not but also able to manipulate the formation rate of an
organic film in a given region, to finally form an organic cap film
of an optional thickness and to selectively adjust the thickness of
an organic film. Please refer to FIG. 1, FIG. 3 to FIG. 4 and FIG.
12; they illustrate a method to manipulate the formation of an
organic film of the present invention. First, please refer to FIG.
1, FIG. 1A and FIG. 1B, a substrate 110, or an article, such as a
bio-catheter, a stent, or a pacemaker is provided. The substrate
110 refers to an object with a large flat surface, such as a test
stripe, and the article refers to an object of a specific 3D shape,
such as a probe. The present invention applies to both the object
with a large flat surface and the object of a specific 3D
shape.
For example, the substrate 110 or the article may be a combination
of an insulator 111 and a conductor 112. The insulator 111 may be
at least one of an insulating material such as plastic, polymer,
rubber, resin, glass and ceramic . . . etc. The conductor 111 may
be at least one of a conductive material such as a metal, an alloy,
a transparent conductive material, conductive rubber, conductive
polymer and graphite . . . etc. To be more specific, the polymer
may be polymethylmethacrylate or polystyrene. The metal may be
titanium, gold or silver. If the substrate 110 or the article is a
combination of an insulator 111 and a conductor 112, the conductor
112 may have a pattern 114 to be embedded in the insulator 111, as
shown in FIG. 1. Or, the conductor 112 may have a pattern 114 to
cover the outer surface 113 of the insulator 111, as shown in FIG.
1A. Or alternatively, the conductor 112 may have a pattern 114
embedded in and covering the insulator 111, as shown in FIG. 1B. No
matter how the arrangements are in FIG. 1, FIG. 1A or in FIG. 1B,
the insulator 111 always makes the conductor 112 exposed. Because
of the combination of the insulator 111 and the conductor 112, the
insulator 111 and the conductor 112 each has its own pattern. The
following description is an example of the substrate 110 with the
conductor 112 of the pattern 114.
Second, as shown in FIG. 2, the substrate 110 is placed in a
reaction chamber 120 to undergo a predetermined polymeric
deposition reaction under a suitable condition with a suitable
precursor 130. The polymeric deposition reaction of the present
invention is a polymeric deposition reaction of the exclusive
combination of an unsubstituted poly-para-xylylene moiety and a
substituted poly-para-xylylene moiety so that the precursor 130 of
the poly-para-xylylene moiety forms an organic film 140 of
poly-para-xylylene on the substrate 110. Accordingly, the suitable
predetermined condition favors the regional inhibition of the
polymeric deposition reaction of poly-para-xylylene so that the
organic film 140 forms a given pattern which selectively covers the
substrate 110 and simultaneously selectively exposes the surface of
the substrate 110, that is, the surface 115 of the conductor 112.
Because the organic film 140 selectively covers the substrate 110,
the process of the precursor 130 of the para-xylylene which forms a
patterned poly-para-xylylene organic film 140 on the substrate 110
may be regarded as the precursor 130 self-aligns with the pattern
114 of the substrate 110 when the precursor 130 undergoes the
predetermined polymeric deposition reaction, which is one of the
features of the present invention.
Or alternatively, a polymeric deposition device illustrated in FIG.
2A may be used to perform the predetermined polymeric deposition
reaction. For example, the precursor 131, the precursor 132 and the
precursor 133 each is fed into the reaction chamber 121 from a
different direction. The device is characterized in that parameters
may be adjusted in according with different starting materials. The
parameters may be one of voltage, a charge density, a deposition
rate and formation time for adjusting selectively inhibition.
The predetermined condition suitable for the polymeric deposition
reaction may be sublimation and followed by pyrolysis of suitable
precursor 130, precursor 131, precursor 132 and precursor 133 to
generate radicals, and the radicals generated in the pyrolysis step
gradually undergo polymeric deposition reaction on the substrate
110 to form the organic film 140 of poly-para-xylylene with a
pattern 141. For example, the reaction chamber 120 has a
sublimation zone 121, a pyrolysis zone 122, and a deposition
chamber 123. The precursor 130, 131, 132 and 133 of unsubstituted
poly-para-xylylene moiety or of substituted poly-para-xylylene
moiety are inhaled from the sublimation zone 121, undergo a
pyrolysis process in the pyrolysis zone 122 to generate radicals,
and the generated radicals then gradually deposit on the substrate
110 placed in the deposition chamber 123 so a structure covered
with a patterned film 140 or a composite structure covered with a
patterned film 140 is resultantly obtained.
The temperature for the sublimation step may be from 100.degree. C.
to 200.degree. C., preferably from 120.degree. C. to 150.degree. C.
The pressure may be from 30 mtorr to 150 mtorr, preferably from 30
mtorr to 100 mtorr. The temperature for the pyrolysis zone may be
from 500.degree. C. to 800.degree. C., preferably from 600.degree.
C. to 700.degree. C. The pressure for the chemical vapor deposition
may be from 30 mtorr to 150 mtorr. The substrate temperature for
the chemical vapor deposition may be from -40.degree. C. to
30.degree. C., preferably from 10.degree. C. to 25.degree. C., more
preferably from 15.degree. C. to 20.degree. C. The deposition rate
of the chemical vapor deposition may be from 0.3 .ANG./s to 20
.ANG./s. The chemical vapor deposition may be a neat reaction to be
free of a catalyst and free of a solvent.
The substituents of the substituted para-xylylene precursor 130 may
be various substituents to imbue the organic film 140 of
poly-para-xylylene with various desirable physicochemical
properties. The substituents may be but not limited to, at least
one of an unsaturated bond, halogen, an aldehyde group, an alkyl
group substituted with a hydroxyl group, a halo-alkyl group, a
4-trifluoroacetyl group, an amino-alkyl group, an amide group, an
amide group comprising a disulfide bond, a carboxyl group, a
biotinyl group, an N-hydroxysuccinimdyl group, an N-maleimide and a
carboxyl anhydride.
The substituted para-xylylene precursor may be a compound
represented by the formula (1). For example, each substituent
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and
R.sub.8 may be independently selected from an ethylenic double
bond, a triple bound, a functional group comprising an amino
(--NH.sub.2) group, a functional group comprising a hydroxyl (--OH)
group, a functional group comprising an carboxyl (--COOH) group,
--C(.dbd.O)H, --C(.dbd.O)--CFH.sub.2, --C(.dbd.O)--CF.sub.3,
--C(.dbd.O)--C.sub.2F.sub.5, --C(.dbd.O)--C.sub.8F.sub.17,
--C(.dbd.O)--OH, --C(.dbd.O)--Ph, --C.ident.CH, --CH.dbd.CH.sub.2,
--CH.sub.2--OH, --CH.sub.2--NH.sub.2, --NH.sub.2,
--C(.dbd.O)--O--CH.sub.3, --C(.dbd.O)--O--C.sub.2H.sub.5,
--CH.sub.2--O--C(.dbd.O)--C--(CH.sub.3).sub.2Br,
--CH.sub.2--O--C(.dbd.O)--C.ident.CH . . . etc. so the organic film
140 may also be a co-polymer consisting of at least one of an
unsubstituted poly-para-xylylene monomer and different substituted
poly-para-xylylene monomers.
In another embodiment of the present invention, the pre-determined
condition further includes a condition for inhibiting the formation
of the organic film 140 or for inhibiting the growth of the organic
film 140 to selectively adjust the thickness of the organic film
140. A condition for inhibiting the formation of the organic film
140 refers to a condition which makes the organic film 140
completely unable to form. A condition for inhibiting the growth of
the organic film 140 refers to a condition which merely makes the
organic film 140 grow slower. Please refer to FIG. 3, inhibiting
the formation of the organic film 140 makes the organic film 140
unable to completely cover the surface 115 of the substrate 110. In
other words, the organic film 140 fails to cover the conductor 112
so the organic film 140 with a given pattern 141 is formed at the
same time. Such given pattern 141 exposes the native surface of the
substrate 110.
Please refer to FIG. 4, although inhibiting the growth of the
organic film 140 still allows the organic film 140 to grow on the
surface 113 of the insulator 111 and on the surface 115 of the
conductor 112, to obtain a substrate 110 completely wrapped inside
the organic film 140 but the thickness of the organic film 140 in
different regions is definitely distinctive to result in a given
pattern 141, namely a given pattern 141 of variable thickness. In
other words, the thickness of the organic film 140 on a product is
not only variable but also can be manipulated to an extent which is
needed. It is another feature of the present invention. The
thickness of the organic film 140 may be from 5 nm to 100
.mu.m.
To adjust the thickness of the organic film 140 may adjust one
parameter or some parameters in combination. The candidate
parameters may be adjusting voltage, adjusting a charge density,
adjusting a deposition rate, adjusting the ingredient of the
precursor, adjusting the formation time of selectively inhibiting,
adjusting the formation temperature of selectively inhibiting and
adjusting the composition of the substrate. When the organic film
140 grows on the insulator 111 and on the conductor 112 to obtain a
given pattern 141 of variable thickness, the thickness of the
organic film 140 on the insulator 111 is usually greater than the
thickness on the conductor 112. This is due to the maximum
selective deposition thickness. No matter the pattern 141 of the
organic film 140 covers the substrate 110 or not, the pattern 141
of the organic film 140 always self-aligns to the pattern 114 of
the substrate 110. It is still another feature of the present
invention.
For example, when the polymeric deposition reaction is carried out
and there are the insulator 111 and the conductor 112 disposed on
the surface of the substrate 110, the conductor 112 may be supplied
with sufficient electric voltage and/or its charge density may be
adjusted to inhibit the growth of the organic film 140 or to
inhibit the formation of the organic film 140 so that the thickness
of the organic film 140 on a product may be selectively adjusted.
No matter a substrate 110 or an article is involved in this
polymeric deposition reaction, it may consist of at least one of an
insulator 111 and a conductor 112 but excludes a semiconductor. A
semiconductor refers to a material which is unable to generate
sufficient electric voltage and/or unable to generate sufficient
charge density and fails to selectively inhibit the formation of
the organic film 140 or fails to selectively adjust the thickness
of the organic film 140 so a semiconductor is not taken into
consideration.
When different insulators 111 go with various conductors 112 to
make up a substrate 110, inhibition of the growth of the organic
film 140 or inhibition the formation of the organic film 140 can be
respectively observed as the conductor 112 is supplied with
different electric voltage and/or charge density. The applied
electric voltage may be from 10 kV to 50 kV, preferably from 20 kV
to 40 kV, more preferably from 30 kV to 35 kV. The applied charge
density may be from 0.01 C/cm.sup.2 (Coulomb/cm.sup.2) to 0.1
C/cm.sup.2, preferably from 0.03 C/cm.sup.2 to 0.06 C/cm.sup.2,
more preferably from 0.045 C/cm.sup.2 to 0.05 C/cm.sup.2.
FIG. 5 and FIG. 5A respectively illustrate the Fourier transform
infrared reflection absorption spectroscopy (IRRAS) spectra of
PPX-C (poly-dichloro-para-xylylene or commercially named parylene
C) and PPX-aldehyde (aldehyde-functionalized poly-para-xylylene) of
the present invention. The precursor of PPX-C and the precursor of
PPX-aldehyde all completely fail to form an organic film on the
surfaces of various metals at a charge density of 0.05 C/cm.sup.2.
FTO refers to fluorine-doped SnO.sub.2(sic passim). The maximum
value of each line in the spectra is regarded as 100% absorption of
each corresponding material involved (sic passim). FIG. 5 and FIG.
5A clearly suggest that the polymeric deposition reaction for
para-xylylene precursors with various substituents is inhibited as
long as a charge density is applied.
FIG. 6 illustrates a correlation of the maximum selective
deposition thickness at different charge densities of the PPX-C
organic film and the PPX-aldehyde organic film of the present
invention. The existence of an upper limit, i.e., a maximum
deposition thickness of the poly-para-xylylene, at which deposition
will commence and the relative selectivity of the charged surface
will be lost, was examined on an Al substrate, which previously
showed no inhibitory effect for poly-para-xylylenes. FIG. 6 clearly
suggests that different charge densities results in different
maximum deposition thickness for the same polymeric material, but
different polymeric materials result in different maximum
deposition thickness at the same charge density. As a result, the
present invention also provides an approach to adjust the needed
thickness of a poly-para-xylylene organic film by providing
different charge densities. Generally speaking, the charge density
increases in proportion to higher maximum deposition thickness.
FIG. 7 illustrates a correlation between the deposition rate of the
PPX-C organic film as well as the PPX-aldehyde organic film and the
maximum selective deposition thickness under the influence of an
electric field of the present invention. FIG. 7 clearly suggests
that a sufficiently high charge density is capable of completely
inhibiting the simultaneous deposition of para-xylylene precursors
with various substituents. Transitional metals, such as Fe, Cu, Ag
and Pt with high surface energy develop superficially inhibiting
influences on the growth of the organic film or on the formation of
the organic film.
In addition to providing different electric voltages and/or charge
density to respectively result in the inhibition of the growth of
the organic film or in the inhibition the formation of the organic
film, adjusting the deposition rate, adjusting the ingredient(s) of
the precursor(s), adjusting the formation time of selectively
inhibiting, adjusting the formation temperature of selectively
inhibiting and adjusting the composition of the substrate may also
possibly result in the influence on the inhibition of the growth of
the organic film or on the inhibition the formation of the organic
film. For example, FIG. 6 also suggests that precursors with
various substituents indeed influence the maximum deposition
thickness of resultant poly-para-xylylene so the thickness of the
organic film 140 may be adjusted by adjusting the ingredient(s) of
the precursor(s).
Further, except providing the substrate with voltage of charge
density, the thickness of the organic film 140 may also be adjusted
by adjusting the deposition rate or adjusting the formation time
during selectively inhibiting. For example, to obtain an organic
film of smaller thickness, the deposition rate may be lower or the
formation time during selectively inhibiting is reduced. In other
words, to obtain an organic film of larger thickness, the
deposition rate may be higher or the formation time during
selectively inhibiting is increased.
The thickness of the organic film may also be adjusted by adjusting
the formation temperature during selectively inhibiting. The change
of the temperature influences the deposition efficiency of the
film, for example higher the temperature lower the deposition rate
is, and vice versa. Moreover, the inventor also notices that the
compositions of the substrate may also influence the formation of
the organic film. For example, FIG. 8 illustrates the deposition
results of the PPX-C organic film of the present invention on
different metal surfaces. FIG. 8A illustrates the deposition
results of the PPX-aldehyde organic film of the present invention
on different metal surfaces. FIG. 8 and FIG. 8A clearly suggest
that Cu and Ag respectively are able to completely inhibit the
deposition of PPX-C film in the absence of the substrate's charge
density but Cu or Ag fails to influence the deposition of
PPX-aldehyde film to yield selective deposition. The uninhibited
deposition thickness of the organic films in each figure is 150
nm.
FIG. 9 illustrates the deposition results of an organic film of
trifluoroacetic-functionalized poly-para-xylylene (PPX-TFA) of the
present invention on different conductor's surfaces in the absence
of the influence of charge density. FIG. 9A illustrates different
deposition results of an organic film of PPX-TFA of the present
invention on different conductor's surfaces in the presence of the
influence of charge density. FIG. 10 illustrates the deposition
results of an organic film of aminomethyl-functionalized
poly-para-xylylene (PPX-amine) of the present invention on
different conductor's surfaces in the absence of the influence of
charge density. FIG. 10A illustrates the different deposition
results of an organic film of PPX-amine of the present invention on
different conductor's surfaces in the presence of the influence of
charge density.
FIG. 9, FIG. 9A, FIG. 10 and FIG. 10A clearly suggest that the
charge density has positive effects on completely inhibiting the
polymeric deposition of an organic film of PPX-TFA or of PPX-amine
although Cu or Ag does not show any influence on the polymeric
deposition of an organic film of PPX-TFA or of PPX-amine. The
uninhibited deposition rate of the organic films in FIG. 9 and FIG.
10 is 300 nm/s with the deposition thickness of around 150 nm.
FIG. 11 illustrates the patterned poly-para-xylylene organic films
which correspond to PPX-TFA, PPX-amine, PPX-aldehyde and PPX-C on a
substrate with patterned Al layer. These figures illustrate the
elemental mapping analysis results of energy dispersive X-ray
spectroscopy (EDS) technique to go with the images from scanning
electron microscopy (SEM). For example, a poly-para-xylylene
organic film of PPX-TFA on a material surface provides a direct
evidence of spatially confined distribution of fluorine signals
(figure b), a poly-para-xylylene organic film of PPX-amine on a
material surface provides a direct evidence of spatially confined
distribution of nitrogen signals (figure c), a poly-para-xylylene
organic film of PPX-aldehyde on a material surface provides a
direct evidence of spatially confined distribution of oxygen
signals (figure d), and a poly-para-xylylene organic film of PPX-C
on a material surface provides a direct evidence of spatially
confined distribution of chlorine signals (figure e). Accordingly,
persons of ordinary skills in the art may have the discretions to
provide suitable parameters to obtain desirable results which meet
expectations when practicing the present invention so the details
will not be elaborated here.
The above steps to manipulate the formation of an organic film of
the present invention may be followed by an optional stripping step
carried out to completely remove the exposed conductor which is not
covered by the organic film. If the conductor 112 is a metal, an
immersing solution containing an oxidizing agent, an acidic
solution or a basic solution, maybe used to strip the metal, as
shown in FIG. 12. If the conductor 112 is a transparent conductive
material, a conventional oxidizing agent or an acidic solution may
go with a suitable surfactant to carry out a wet etching stripping
procedure.
After the above steps of the present invention, an optional
patterned film structure or an optional patterned film composite
structure is obtained. FIG. 13 illustrates a patterned film
structure 100 without a conductor 112 after the above stripping
procedure. FIG. 14 illustrates a patterned film composite structure
101 with the organic film 140 not covering the conductor 112. FIG.
15 illustrates a patterned film structure 102 with a conductor 112
sandwiched between the insulator 111 and the organic film 140 so in
the patterned film structure 100, the patterned film composite
structure 101 and the patterned film structure 102 of the present
invention, there are a substrate 110 and a patterned polymeric
layer 140.
The insulator 111 to go with the conductor 112 forms the substrate
110. The patterned polymeric layer 140 has the pattern 141
transferred from the conductor 112 to selectively cover the
substrate 110. Or to say, the patterned polymeric layer 140 at
least completely covers the surface 113 of the insulator 111, and
may further optionally cover the surface 115 of the conductor 112.
The pattern 141 may come in various designs, such as a grid pattern
with an extremely small pitch or line width, a geometric pattern,
an asymmetric pattern, an irregular pattern, an isolated pattern or
repetitive patterns . . . etc.
The patterned polymeric layer 140 consists of at least one of an
unsubstituted poly-para-xylylene and a substituted
poly-para-xylylene. In one embodiment of the present invention, the
patterned polymeric layer 140 exclusively consists of an
unsubstituted poly-para-xylylene. In another embodiment of the
present invention, the patterned polymeric layer 140 exclusively
consists of a substituted poly-para-xylylene. In still another
embodiment of the present invention, the patterned polymeric layer
140 consists of an unsubstituted poly-para-xylylene and a
substituted poly-para-xylylene.
The substituents of the substituted para-xylylene may be various
substituents to imbue the organic film 140 of poly-para-xylylene
with desirable physicochemical properties. The substituents may be
but not limited to, at least one of an unsaturated bond, halogen,
an aldehyde group, an alkyl group substituted with a hydroxyl
group, a halo-alkyl group, a 4-trifluoroacetyl group, an
amino-alkyl group, an amide group, an amide group comprising a
disulfide bond, a carboxyl group, a biotinyl group, an
N-hydroxysuccinimdyl group, an N-maleimide and a carboxyl
anhydride.
The substituted para-xylylene precursor 130 may be a compound
represented by the Formula (1) in FIG. 16. Formula (1) shows the
substituted poly-para-xylylenes of the present invention. For
example, each substituent R.sub.1, R.sub.2, R.sub.3, R.sub.4,
R.sub.5, R.sub.6, R.sub.7, R.sub.8 may be independently selected
from an ethylenic double bond, a triple bound, a functional group
comprising an amino (--NH.sub.2) group, a functional group
comprising a hydroxyl (--OH) group, a functional group comprising
an carboxyl (--COOH) group, --C(.dbd.O)H, --C(.dbd.O)--CFH.sub.2,
--C(.dbd.O)--CF.sub.3, --C(.dbd.O)--C.sub.2F.sub.5,
--C(.dbd.O)--C.sub.8F.sub.17, --C(.dbd.O)--OH, --C(.dbd.O)--Ph,
--C.ident.CH, --CH.dbd.CH.sub.2, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --NH.sub.2, --C(.dbd.O)--O--CH.sub.3,
--C(.dbd.O)--O--C.sub.2H.sub.5,
--CH.sub.2--O--C(.dbd.O)--C--(CH.sub.3).sub.2Br,
--CH2-O--C(.dbd.O)--C.ident.CH . . . etc. so the organic film 140
may also be a co-polymer consists of different substituted
poly-para-xylylene monomers.
When the substrate 110 is an insulator 111, such as what is
illustrated in FIG. 3, the patterned polymeric layer 140 covers
part of the surface 113 of the substrate 110, and the pattern 114
selectively exposes the surface 116 of the substrate 110. In one
embodiment of the present invention, when the insulator 111 goes
with the conductor 112 to form the substrate 110, please refer to
FIG. 14, the patterned polymeric layer 140 covers the surface 113
of the substrate 110 but the pattern 141 exposes the surface 115 of
the conductor 112. In another embodiment of the present invention,
the patterned polymeric layer 140 covers the surface 113 of the
insulator 111 as well as the surface 115 of the conductor 112, a s
shown in FIG. 15. The thickness of the patterned polymeric layer
140 may be 5 nm to 100 .mu.m.
When the patterned polymeric layer 140 covers the surface 115 of
the conductor 112, the thickness of the patterned polymeric layer
140 on the insulator 111 is usually greater than the thickness of
the patterned polymeric layer 140 on the conductor 112. This is due
to the above-mentioned maximum selective deposition thickness to
cause the pattern 141, and it is one of the features of the present
invention. No matter the pattern 141 of the polymeric layer 140
completely covers the substrate 110 or not, the pattern 141 of the
polymeric layer 140 always self-aligns to the substrate 110, to the
surface 113 of the insulator 111, to the pattern 114 of the
substrate 110, to the surface 115 of the conductor 112 or to the
pattern 116 of the substrate 110. It is another outstanding feature
of the present invention.
The following examples of synthesis and experimental embodiments
are provided to more comprehensively describe the gist of the
present invention but the scope of the present invention is not
limited to these following examples or to these following
embodiments.
Embodiment 1
First, 4-N-maleimidomethyl-[2,2]paracyclophane 4 is synthesized.
Reaction (1) shows the synthesis of 4-N-maleimidomethyl-[2,2]
paracyclophane. Referring to Reaction (1) in FIG. 17, in a nitrogen
environment, titanium (IV) chloride (TiCl.sub.4) (8.4 mL, 77 mmol)
is added slowly to a market-purchased solution of
[2,2]paracyclophane 1 (8.0 g, 38 mmol) in anhydrous
CH.sub.2Cl.sub.2 (400 mL). The mixture is stirred for 20 minutes,
followed by the dropwise addition of .alpha.,.alpha.-dichloromethyl
methyl ether (CHCl.sub.2OCH.sub.3) (4.0 mL, 44 mmol) at room
temperature.
The mixture is then continuously stirred for 6 hours to perform a
Rieche formylation. Then, the mixture is poured into water (200 mL)
and stirred for another 2 hours. The solution is washed with 3M HCl
(2.times.300 mL) and then with water (2.times.300 mL), and dried
over MgSO.sub.4.
After filtration and removal of the solvent, the crude product is
purified using hexane/dichloromethane (5/1) as eluent to yield
4-formyl-[2,2]paracyclophane 2 as crystals (6.6 g, 83%). The
crystals are dissolved in a mixture of MeOH (200 mL) and anhydrous
Tetrahydrofuran (THF) (10 mL). Then, sodiumborohydride (NaBH.sub.4)
(2.1 g, 28 mmol) is added carefully and the mixture is stirred at
room temperature for 3 hours. The excess NaBH.sub.4is then
decomposed by addition of water.
The resulting solution is then diluted by ethyl acetate (200 mL),
washed with 3M HCl (3.times.200 mL) and water (2.times.200 mL), and
dried over MgSO.sub.4. After filtration and removal of the solvent,
4-(hydroxymethyl)-[2,2]paracyclophane 3 is obtained as crystals
(6.0 g, 75%).
Next, the resulting 4-(hydroxymethyl)-[2,2]paracyclophane 3 (6.0 g)
and triphenylphosphine (PPh.sub.3) (13.1 g) are dissolved in
anhydrous THF, to which diisopropyl azodicarboxylate (DIAD) (10 mL)
is added carefully and the mixture is stirred at room temperature
for 20 minutes. Then, a previously prepared maleimide solution (4.9
g maleimide in 30 mL anhydrous THF) is added to the resulting
mixture and stirred at room temperature for 24 hours. The solution
is then diluted with dichloromethane (200 mL), washed with 3M HCl
(3.times.200 mL) and water (2.times.200 mL), and dried over
MgSO.sub.4. The crude product is purified using hexane/ethyl
acetate (5/1) to yield 4-N-maleimidomethyl-[2,2]paracyclophane 4 as
crystals (5.2 g, 65%).
Then, poly[(4-N-maleimidomethyl-p-xylylene)-co-(p-xylylene)] 5 is
prepared from 4-N-maleimidomethyl-[2,2]paracyclophane 4 with a CVD
polymerization process, wherein m:n=1:1. Throughout the process, a
constant argon flow rate of 10 s.c.c.m. and a system pressure of 75
mTorr are maintained. The sublimation temperature is set between
110.degree. C. and 120.degree. C., and the pyrolysis temperature is
set at 580.degree. C. Under these conditions, CVD polymerization
occurs spontaneously on substrates that are placed on a rotating,
cooled (15.degree. C.) sample holder.
A deposition rate of about 0.3 .ANG./s is monitored on the basis of
in situ quartz crystal microbalancing analysis. Moreover, using an
ellipsometer, the thickness of the resulting
maleimide-functionalized poly-p-xylylene coating deposited is
measured in the range of 60 nm to 80 nm. Generally speaking, the
unsubstituted poly-para-xylylene monomer and different substituted
poly-para-xylylene monomers are polymerized in a random way.
Embodiment 2
First, the device as shown in FIG. 2A is used to feed the starting
material 4-ethynyl-[2,2]paracyclophane, the starting material
4-N-maleimidomethyl-[2,2]paracyclophane and the starting material
trifluoroacetyl-[2.2]paracyclophane from different directions into
the reaction chamber 120. The starting material
4-ethynyl-[2,2]paracyclophane,
4-N-maleimidomethyl-[2,2]paracyclophane and
trifluoroacetyl-[2.2]paracyclophane are provided in a 1:1:1
ratio.
In addition, as shown in FIG. 2A, before entering the reaction
chamber 120, the three starting material each passes through
several pre-treating units. The pre-treating units maybe a
sublimation zone (about 105.degree. C.) or a pyrolysis zone 122
(about 70.degree. C.). Furthermore, there is a silicon material
substrate 110 in the reaction chamber 120 to control the
temperature about 20.degree. C. at 2 rpm/min.
After the starting materials are fed into the reaction chamber 120,
the co-polymer
poly[(4-ethynyl-p-xylylene)-co-(4-N-maleimidomethyl-p-xylylene)-co-(trifl-
uoroacetyl-p-xylylene)-co-(p-xylylene)] organic film 140 is
obtained on the silicon material substrate 110 from the
polymerization of the starting materials by chemical vapor
deposition in accordance with Reaction 2 in FIG. 17. Generally
speaking, each para-xylylene monomer is polymerized in a random
way.
Embodiment 3
Infrared reflection-absorption spectroscopy (IRRAS) is used to
analyze the co-polymer organic film 140 with the above three
functional groups, and the spectrum of the co-polymer (IV) organic
film 140 is individually compared with the reference spectrum of
poly[(4-ethynyl-p-xylylene)-co-(p-xylylene)] (I),
poly[(4-N-maleimidomethyl-p-xylylene)-co-(p-xylylene)] (II), and
poly[(trifluoroacetyl-p-xylylene)-co-(p-xylylene)] (III) (in short,
each reference spectrum has only one target functional group).
The spectrum in FIG. 18 shows that the spectrum of the co-polymer
(IV) organic film 140 has two strong peaks in the region 3289
cm.sup.-1 and 2102 cm.sup.-1 corresponding to the terminal
acetylene, another two strong peaks in the region 1768 cm.sup.-1
and 1709 cm.sup.-1 corresponding to the carbonyl bond (C.dbd.O) of
the maleimidomethyl group and trifluoroacetyl group, another strong
peak in the region 1402 cm.sup.-1 corresponding to the C--N--C bond
of the maleimidomethyl group and other strong peaks in the region
1223 cm.sup.-1, 1194 cm.sup.-1, 1150 cm.sup.-1, and 981 cm.sup.-1
corresponding to the C--F bond of the trifluoroacetyl group.
Embodiment 4
X-ray photoelectron spectroscopy is used to analyze the co-polymer
organic film 140 to obtain the results listed in Table 1 in FIG.
19. Table 1 shows the X-ray photoelectron spectroscopy of the
co-polymer organic film. Please refer to Table 1, the experimental
values are consistent with the calculated theoretical values which
are derived from the monomer units of equal molar ratios.
Embodiment 5
A paracylophane film containing functional group with disulfide
bond, such as a paracylophane with thiol-disulfide carboxylic acid
end group is provided. In the following paragraphs, each step of
the method will be further detailed using
(4-(3-((3-methylamido)-disulfide)propanoic acid)[2,2]
paracyclophane as an example. It is noted that the chemical
manufacturing company described below is only one example in the
present invention and is not to the limitation to the scope the
claimed invention.
Five steps are needed for the synthesis of
4-(3-((3-Methylamido)disulfide)propanoic acid) [2,2]paracyclophane
from commercially available [2,2]paracyclophane (Sigma-Aldrich, St.
Louis, Mo., USA). Titanium(IV) chloride (8.4 mL, 77 mmol)
(Sigma-Aldrich) was added slowly to an ice-cooled solution of
[2,2]paracyclophane (8.0 g, 38 mmol) in anhydrous CH.sub.2Cl.sub.2
(400 mL) under a nitrogen environment. The mixture was stirred for
20 min, followed by the dropwise addition of
.alpha.,.alpha.-dichloromethyl methyl ether (4.0 mL, 44 mmol;
Sigma-Aldrich). The reaction mixture was stirred at room
temperature for 6 h, subsequently poured into water, and then
stirred for an additional 2 h (200 mL). Next, the organic layer was
washed with 3 M HCl (2.times.300 mL) and then with water
(2.times.300 mL), after which it was dried over MgSO.sub.4. After
filtration and removal of the solvent, the crude product was
purified on silica gel using hexane/CH.sub.2Cl.sub.2 (5/1) as the
eluent to yield 4-formyl[2,2]paracyclophane as white crystals (6.6
g, 83%).
The crystals were then dissolved in a mixture of MeOH (200 mL) and
anhydrous tetrahydrofuran (THF; 10 mL). NaBH.sub.4 (2.1 g, 28 mmol;
Sigma-Aldrich) was added carefully to this solution, and the
mixture was stirred at room temperature for 3 h. The excess
NaBH.sub.4 was then decomposed by the careful addition of water.
The solution was then diluted with EtOAc (200 mL), washed with 3 M
HCl (3.times.200 mL) and then with water (2.times.200 mL), and
dried over MgSO.sub.4. After filtration and removal of the solvent,
4-hydroxymethyl[2,2]paracyclophane was obtained as white crystals
(6.0 g, 75%), which were used without further purification. The
4-hydroxymethyl[2,2]paracyclophane was dissolved in anhydrous
CH.sub.2Cl.sub.2 (200 mL) and cooled to 0.degree. C. under a
nitrogen environment.
Next, PBr.sub.3 (3.00 mL, 31.8 mmol; Sigma-Aldrich) was added
dropwisely, and the mixture was stirred for 4 h. The reaction was
hydrolyzed by the addition of water (150 mL), and the phases were
separated. The organic layer was washed with 1 M HCl (150 mL),
saturated NaHCO.sub.3 solution (150 mL), and saturated NaCl
solution (150 mL). It was then dried over MgSO.sub.4 and filtered,
after which the solvent was removed in vacuum. The crude product
4-bromomethyl[2,2] paracyclophane (5.81 g, 77%) was used in the
next step without further purification.
Crude 4-bromomethyl[2,2]paracyclophane and potassium phthalimide
(3.71 g, 20.0 mmol; Sigma-Aldrich) were dissolved in
dimethylformamide (100 mL) and heated to 80.degree. C. for 4 h.
After complete conversion (TLC control), the solvent was removed in
vacuum and the residue was dissolved in EtOAc (500 mL) and washed
with saturated NaCl solution (400 mL). The aqueous phase was
extracted with CH.sub.2Cl.sub.2 (2.times.200 mL), and the combined
organic phases were dried over MgSO.sub.4. After removal of the
solvent, the crude product (7.06 g) was dissolved in MeOH (300 mL)
and hydrazine (19 mL, 80% in water; Sigma Aldrich) was added. The
reaction mixture was heated to 60.degree. C. for 1 h (TLC control).
Next, the solvent was removed, and the residue was taken up in
CH.sub.2Cl.sub.2 (500 mL) and 1 M NaOH solution (300 mL). The
phases were separated, and the aqueous phase was extracted with
CH.sub.2Cl.sub.2 (300 mL). The combined organic phases were washed
with 1 M NaOH (300 mL) and brine (300 mL). The organic phase was
dried over MgSO.sub.4, and the solvent was removed in vacuum. The
crude product was purified on silica gel using
CH.sub.2Cl.sub.2/MeOH (9/1) to yield
4-aminomethyl[2,2]paracyclophane (2.57 g, 56%).
Next, 3,3'-dithiodipropionic acid (2.10 g, 10 mmol; Sigma-Aldrich)
and N-ethyl-N'-(3-(dimethylamino)propyl)carbodiimide (EDC; 1.55 g,
10 mmol; Alfa Aesar, Ward Hill, Mass., USA) were dissolved in
anhydrous THF (250 mL) and stirred at room temperature for 20 min.
4-aminomethyl[2,2]paracyclophane (2.37 g) was added to the
resulting solution and reacted at room temperature for 12 h. The
reaction product was washed with saturated NaHCO.sub.3 solution
(3.times.500 mL) and dried over MgSO.sub.4. The crude product was
purified on silica gel using hexane/ethyl acetate (5/1) to yield
4-(3-((3-methylamido)-disulfide)propanoic acid) [2,2]paracyclophane
as white crystals (2.71 g, 63%).
The following parameters were obtained from NMR, FT-IR, and ESI-MS
analyses of the product. Please refer to FIG. 20, FIG. 21, FIG. 22
and FIG. 23. FIG. 20 is a .sup.1H NMR spectrum, FIG. 21 is a
.sup.13C NMR spectrum, FIG. 22 is a FT-IR spectrum, and FIG. 23 is
an ESI-MS spectrum of 4-(3-((3-methylamido)-disulfide)propanoic
acid) [2,2]paracyclophane. As shown in FIG. 20, the parameters of
.sup.1H NMR: (500 MHz, CDCl.sub.3, TMS): .delta. 6.67-6.69 (2d,
J=1.9 Hz, 1.9 Hz, 1H), 6.36-6.50 (m, 5H), 6.21 (d, J=1.40 Hz, 1H),
5.71 (s, 1H), 4.35-4.40 (2d, J=5.3 Hz, 5.3 Hz, 1H), 4.09-4.13 (2d,
J=5.2 Hz, 5.2 Hz, 1H), 2.72-3.47 (m, 16H), 2.52-2.55 (t, J=14.1 Hz,
2H). As shown in FIG. 21, the parameters of .sup.13C NMR (125 MHz,
CDCl.sub.3, TMS): .delta. 32.9, 33.0, 33.6, 33.8, 34.3, 34.9, 35.2,
35.7, 42.8, 129.1, 132.1, 132.2, 133.1, 133.2, 133.8, 135.1, 136.4,
138.0, 139.2, 139.3, 140.5, 170.8, 175.8. As shown in FIG. 22, the
parameters of FT-IR: 3291 (m), 3024 (w), 2924 (m), 2853 (w), 1704
(s), 1668 (s), 1621 (m), 1520 (w), 1513 (m), 1444 (m), 1419 (m),
1332 (w), 1231 (w), 1204 (w), 1181 (w), 1041 (m), 940 (vw), 890
(vw), 823 (m), 762 (vw), 725 (vw), 624 (vw), 548 (w), 519 (m), 492
(w). As shown in FIG. 23, the parameters of ESI-MS: m/z (%) 428.15
(100) [M+]. With such spectrum data, it is demonstrated that the
method of according to the present invention can obtain
4-(3-((3-methylamido)-disulfide)propanoic acid) [2,2]paracyclophane
as products.
Afterwards, the obtained paracyclophane containing a disulfide
functional group can be further polymerized in accordance with
Reaction (3) in FIG. 17, and then coated on a substrate through a
chemical vapor deposition (CVD) process to form a chemical film
comprising N-hydroxysuccinimide ester-functionalized
poly-p-xylylene. Reaction (3) shows the obtained paracyclophane
containing a disulfide functional group can be further polymerized.
In one preferred embodiment, R is a functional group containing
disulfide bond, such as a derivative containing an
amide-thiol-disulfide carboxylic acid functional group, and in one
preferred embodiment, R is 4-(3-((3-methylamido)-disulfide)
propanoic acid. Generally speaking, the unsubstituted
poly-para-xylylene monomer and different substituted
poly-para-xylylene monomers are polymerized in a random way.
Those skilled in the art will readily observe that numerous
modifications and alterations of the device and method may be made
while retaining the teachings of the invention. Accordingly, the
above disclosure should be construed as limited only by the metes
and bounds of the appended claims.
* * * * *
References